1. Field of the Invention
The invention relates to new 1-aryl-5-(substituted alkyl(thio)amido)pyrazoles and to processes for their preparation. The invention further pertains to compositions of said compounds and methods, using said compounds, for the control of arthropod, nematode, helminth or protozoan pests. In particular it relates to the application of said compounds or compositions in agricultural methods of use, particularly as pesticides, for controlling arthropods, especially insects via ingestion or contact action.
2. Description of the Related Art
Various 1-(substituted phenyl or pyridyl)-5-(substituted alkyl(thio)amido) pyrazole compounds are known to exhibit a number of different types of pesticidal activity, including activity as herbicides, plant growth regulators, insecticides, and nematicides. Included among these are the following:
EP 295,117; WO 87/03781 (also corresponding to EP 234,119); EP 295,118; and EP 350,311 disclose 1-phenyl-5-(substituted amino)pyrazole compounds for control of arthropod, nematode, helminth and protozoan pests. PA0 GB 2, 136,427 discloses as herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)-4-cyanopyrazoles, which are unsubstituted at the 3-position of the pyrazole ring. PA0 U.S. Pat. No. 4,772,3 12 discloses as herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl substituted in the 3-position of the pyrazole ring. PA0 U.S. Pat. No. 4,804,675 discloses as insecticides, acaricides, and nematicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl or haloalkyl substituted in the 3-position of the pyrazole ring. PA0 U.S. Pat. No. 4,740,232 discloses as herbicides 1-(substituted phenyl)-5-(substituted amino)pyrazole compounds, which are unsubstituted in the 3-position of the pyrazole ring. PA0 EP 398,499 discloses phenyl substituted heterocyclic compounds as insecticides and acaricides, including 1-(substituted phenyl)-5-(substituted amino)pyrazoles. PA0 EP 335,156 discloses as herbicides 1-aryl-5-(substituted amino)pyrazoles, which are H or alkyl at the 3-position, and H, NO.sub.2,COOH, alkoxycarbonyl at the 4-position of the pyrazole ring; CA 112(19):178967q. PA0 JP 63,313,773 discloses as herbicides and microbicides 1-(aryl or alkyl)-5-[(phenoxy- or 2-pyridyloxyalkylacyl)-amino]pyrazoles; CA 111(15):134141r. PA0 EP 302,328 discloses as herbicides and plant growth regulators 1-aryl-5-(substituted amino)pyrazoles, which is H at the 3-position and H or NO.sub.2 at the 4-position of the pyrazole ring; CA 110(25);231624n. PA0 DE 3,603,291 discloses as herbicides and plant growth regulators 1-[4-(trifluoromethyl)tetrafluorophenyl]pyrazoles, which is H, NO.sub.2, NO, halo, (modified)carboxylates, acyl, amido at the 4-position, and H or alkyl at the 3-position of the pyrazole ring; CA 110(15):135237t. PA0 JP 63,174,905 discloses as fruit thinning agents 1-aryl-5-(substituted amido)pyrazoles; CA 110(11):90608w. PA0 DE 3,707,551 discloses as herbicides N-(substituted acyl)-1-aryl-1H-pyrazol-5-amines with N, NO.sub.2 at the 4-position of the pyrazole ring: CA 110(5):38991 b. PA0 DE 3,618,717 discloses as herbicides 1-aryl-5-(substituted acylamino)pyrazoles with H, NO.sub.2, halo at the 4-position and H at the 3-position of the pyrazole ring; CA 108(15): 131809s. PA0 DE 3,600,950 discloses as herbicides 5-(alkanoylamino)-1-arylpyrazoles with H, NO.sub.2, halo at the 4-position and H at the 3-position of the pyrazole ring; CA 108(3):21880a. PA0 JP 62, 153,283 discloses as herbicides and antimicrobials .alpha.-[(pyridyloxy)alkyl]-N-pyrazolylacetamides; CA 107(23):217623t. PA0 JP 62,153,273 discloses as bactericides, herbicides and fungicides .alpha.-[(phenoxy)alkyl]-N-pyrazolyl acetamides; CA 107(21 ): 198317c. PA0 JP 62,138,475 discloses as herbicides, fungicides and bactericides [(phenoxyalkanoyl)amino]pyrazole derivatives; CA 107(19): 176028g. PA0 DE 3,420,985 discloses as herbicides 5-(substituted acyl)amino- 1-phenylpyrazoles with H at the 3-position and cyano, alkylcarbonyl group at the 4-position of the pyrazole ring; CA 104(3): 19599q. PA0 JP 47,031,979 discloses as antipyretic, analgesic, anti-inflammatory, diuretic and tranquilizing agents 5-[.alpha.-(substituted aminoacetamido)]pyrazoles with benzoyl group at the 4-position; CA 78(5):29769d. PA0 DE 3,911,556 discloses as pesticides 1-aryl-4-alkylthio-5-aminopyrazoles and related compounds, which are unsubstituted or substituted with alkyl at the 3-position of the pyrazole ring; CA 114(15): 143412u. PA0 Farmaco, 44(9), 809-18 (1989). [CA 112(19):172137x]discloses 1-aryl-5-[substituted amido]pyrazoles as intermediates for pyrazole [3,4-e][1,4]diazepine-4,7-dione derivatives with central nervous system activity. PA0 Indian J. Chem., Sect. B, 27B(6), 602-4 (1988), [CA 109(23):210945g]. Synthesis and pharmacological activities of 5-(aminoacetylamino)-4-carbethoxy-1-phenyl pyrazoles. PA0 Farmaco, Ed. Sci., 37(7), 450-8 (1982), [CA 97(19): 163463v] discloses as antifungal substances amides of amino acids and peptides of 5-aminopyrazole with phenyl at the 1-position, methyl at the 3-position and thiocyanate at the 4-position of the pyrazole ring. PA0 EP 308,885 discloses as cholecystokinin antagonists 1,3-phenyl-(5-substituted amido)pyrazoles; [CA 111(15):134747t]. PA0 DE 3,637,710 discloses as herbicides 5-(substituted acylamino)pyrazole with H, NO.sub.2, at the 4-position of the pyrazole ring; [CA 109(19):165721t]. PA0 JP 54,046,780 discloses as gastric acid secretion inhibitors 1-phenyl-(5-substituted amido)pyrazoles; [CA 91(23): 193 185z]. PA0 Gazz. Chim. Ital., 103 (10-12), 1113-21 (1973) [CA 81(21):136468p]discloses the synthesis of a group of 1-phenyl, 3-methyl, 4-nitroso, 5-(substitute amido)pyrazoles. PA0 R.sup.2 is: halogen; alkyl; haloalkyl; alkoxy; haloalkoxy; nitro; thiocyanato; unsubstituted or mono- or dialkyl substituted sulfamoyl; unsubstituted or mono- or dialkyl substituted aminocarbonyl; alkoxycarbonyl; or unsubstituted or substituted R.sup.11 S(O).sub.n, in which n is 0, 1 or 2 and R.sup.11 is alkyl, haloalkyl, cycloalkyl, halocycloalkyl, cycloalkylalkyl or halocycloalkylalkyl; and wherein the alkyl moleties are linear or branched chains of 1-4 carbon atoms, the cycloalkyl moiety contains 3 to 7 carbon atoms and the halo substitution consists of one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and cycloalkyl moleties; PA0 R.sup.7 is hydrogen, halogen or linear or branched chain C.sub.1-8 alkyl, alkoxy; PA0 R.sup.8 and R.sup.10 are each individually hydrogen or fluorine; PA0 Y is O, S; PA0 R.sub.3 is H, alkyl, alkoxyalkyl, propargyl, allyl, alkoxycarbonyl, benzyl, alkylcarbonyl, ##STR3## R.sub.4 is H, alkyl, haloalkyl, halogen, phenyl, optionally substituted with halogen, alkyl, alkoxy, haloalkoxy, cyano, nitro, and haloalkyl; PA0 R.sub.5 is H, alkyl, haloalkyl, halogen, haloalkoxyalkyl, alkyl S(O)z alkyl [z=0, 1, 2], alkoxy (alkoxy).sub.a alkyl (a=0-4), OH, alkyl OC(O) alkyl, and alkoxy; PA0 R.sup.4 and R.sup.5 could be together to form a 3-7 membered cyclic ring system with 0-2 heteroatoms (e.g. O, S, S(O), S(O).sub.2, NH, N-alkyl), N--C(O)alkyl, N--C(O)-haloalkyl; PA0 R.sub.6 is alkoxy, haloalkoxy, alkoxy(alkoxy).sub.b [b=1-4], alkoxy(alkoxy).sub.b alkyl [b=0-4], haloalkoxy(alkoxy).sub.b alkyl [b=0-4], haloalkoxy(alkoxy).sub.b [b=1-4], alkylS(O).sub.c (c=0, 1, 2), haloalkylS(O).sub.c [c=0, 1, 2], hydroxy, alkylS(O).sub.c alkyl [c=0, 1, 2], alkylC(O)Oalkyl, hydroxyalkyl, OC(O)alkyl, R.sub.13 C(O)--, R.sub.13 C(O)alkyl [R.sub.13 =--OH, --O.sup..crclbar. M.sup..sym. (M.sup..sym. =Na.sup.+, Ca.sup.+2, K.sup.+, tetraalkylammonium), --NH.sub.2, alkoxy, monoalkylamino, dialkylamino, alkyl, haloalkyl, phenyl or pyridyl optionally substituted by halogen, alkyl, alkoxy, CN, nitro, haloalkyl, haloalkoxy]; nitro; nitroalkyl; cyano; cyanoalkyl; amino; monoalkylamino; dialkylamino; (alkyl).sub.3 N.sup.+ ; mono(haloalkyl)amino; di(haloalkyl)amino; morpholino; piperazino; dialkylamino oxide; monoalkylamino oxide; N-alkylpiperazino; aminoalkyl; monoalkylaminoalkyl; dialkylaminoalkyl; di(alkyl)N.sup.+ (.fwdarw.O)alkyl; (alkyl).sub.3 N.sup.+ alkyl; morpholinoalkyl; piperazinoalkyl; N-alkylpiperazinoalkyl; phenoxy, phenylS(O).sub.c, phenoxyalkyl, phenylS(O).sub.c alkyl, phenylalkoxy, phenylalkoxyalkyl, pyridyloxy, pyridylS(O).sub.c, pyridyloxyalkyl, pyridylS(O).sub.c alkyl, pyridylalkoxy, pyridylalkoxyalkyl, optionally substituted with alkyl, halogen, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, alkylthio, [c =0, 1, 2]; PA0 R.sup.5 and R.sup.6 could be together to form a 4-7 membered cyclic ring with 1-2 heteroatoms (e.g. O, S, S(O), S(O).sub.2, NH, N-alkyl), or a 4-7 membered lactone or lactam or N-alkyl lactam; PA0 R.sup.4, R.sup.5 and R.sup.6 could be together to form a bicyclic [3, 2, 2] or [2, 2, 2] or [2, 2, 1] system with 1-3 heteroatoms, (e.g. O, S, S(O), S(O)2, NH, N-alkyl; PA0 R.sup.9 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkyl-S(O).sub.n or haloalkyl-S(O).sub.n in which n is 0, 1 or 2; and wherein the alkyl and alkoxy moleties are linear or branched chains of 1-4 carbon atoms and the halo substitution consists of one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and alkoxy moieties; and PA0 X is a nitrogen atom (N) or C--R.sup.12 in which R.sup.12 is hydrogen, halogen, cyano, nitro, C.sub.1-8 alkyl, alkylthio or alkoxy; and the alkyl moleties are linear or branched chains. PA0 R.sup.1 is cyano or halogen; PA0 R.sup.2 is unsubstituted or substituted R.sup.11 S(O).sub.n, in which n is 0, 1 or 2 and R.sup.11 is alkyl or haloalkyl as defined, NO.sub.2 ; PA0 R.sup.3 is hydrogen or alkyl; PA0 R.sup.7 is hydrogen, halogen or alkyl; PA0 R.sup.8 and R.sup.10 are each individually hydrogen or fluorine; PA0 R.sup.9 is halogen, alkyl, haloalkyl or haloalkoxy; PA0 Y is O; PA0 R.sub.4 is H, alkyl, phenyl, optionally substituted with halogen, alkyl, alkoxy, haloalkoxy, cyano, nitro, or haloalkyl; PA0 R.sub.5 is H or alkyl; PA0 R.sup.4 and R.sup.5 could be together to form a 3-7 membered cyclic ring system; PA0 R.sub.6 is alkoxy, haloalkoxy, alkoxy(alkoxy).sub.b [b=1-4], alkoxy(alkoxy).sub.b alkyl [b=0-4], haloalkoxy(alkoxy).sub.b alkyl [b=0-4], haloalkoxy(alkoxy).sub.b [b=1-4], alkylS(O).sub.c (c=0, 1, 2), haloalkylS(O).sub.c [c=0, 1, 2], alkylS(O).sub.c alkyl [c=0, 1, 2], alkylC(O)Oalkyl, hydroxyalkyl, OC(O)alkyl, alkylC(O)--; alkyl(CO)alkyl; amino,; monoalkylamino; dialkylamino; (alkyl).sub.3 N.sup.+ ; morpholino; piperazino; N-alkylpiperazino; aminoalkyl; monoalkylaminoalkyl; dialkylaminoalkyl; (alkyl).sub.3 N.sup.+ alkyl; morpholinoalkyl; piperazinoalkyl; N-alkylpiperazinoalkyl; phenoxy, phenylS(O).sub.c, phenoxyalkyl, phenylS(O).sub.c alkyl, phenylalkoxy, phenylalkoxyalkyl, pyridyloxy, pyridylS(O).sub.c, pyridyloxyalkyl, pyridylS(O).sub.c alkyl, pyridylalkoxy, pyridylalkoxyalkyl, optionally substituted with alkyl, halogen, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, alkylthio, [c=0, 1, 2]; PA0 R.sup.5 and R.sup.6 could be together to form a 4-7 membered cyclic ring with 1-2 heteroatoms (e.g. O, S, S(O), S(O).sub.2, NH, N-alkyl) or a 4-7 membered lactone, lactam or N-alkyl lactam; and PA0 X is a nitrogen atom (N) or C--R.sup.12 in which R.sup.12 is hydrogen, halogen, cyano, alkyl, alkylthio or alkoxy. PA0 R4 is H or alkyl; PA0 R5 is H or alkyl; PA0 R.sup.4 and R.sup.5 could be together to form a 3-7 membered cyclic ring system; PA0 R.sub.6 is alkoxy, alkoxy(alkoxy).sub.b [b=1-2], alkoxy(alkoxy).sub.b alkyl [b=0-2], alkylS(O).sub.c (c=0, 1, 2), alkylS(O).sub.c alkyl [c=0, 1, 2], alkylC(O)--; phenoxy, phenylS(O).sub.c, phenylalkoxy, pyridyloxy, pyridylS(O).sub.c, optionally substituted with alkyl, halogen, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, alkylthio [c=0, 1, 2]. PA0 R.sup.5 and R.sup.6 could be together to form a 4-7 membered cyclic ring with 1-2 heteroatoms (e.g. O, S, S(O), S(O).sub.2, NH, N-alkyl); PA0 R.sup.7 is: hydrogen; alkyl, preferably methyl; or halogen, preferably F, Cl or Br; PA0 R.sup.9 is: halogen, preferably F, Cl or Br; alkyl, preferably methyl; haloalkyl, preferably trihalomethyl and more preferably trifluoromethyl; or haloalkoxy, preferably trihalomethoxy and more preferably trifluoromethoxy; and in which halo is F, Cl or Br or combinations thereof; and PA0 X is a nitrogen atom or C--R.sup.12 in which R.sup.12 is: hydrogen; halogen, preferably F, Cl or Br; cyano; alkyl, preferably methyl or ethyl; alkylthio, preferably methylthio or ethylthio; or alkoxy, preferably methoxy or ethoxy.
It is thus apparent that the nature and position of substituent groups on a pyrazole ring provide widely different types of biological activity which type and level of activity is not readily apparent.